CN111533086B - Short-flow preparation method for rapidly activating hydrogen storage alloy by utilizing hydrogen-containing compound - Google Patents
Short-flow preparation method for rapidly activating hydrogen storage alloy by utilizing hydrogen-containing compound Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000001257 hydrogen Substances 0.000 title claims abstract description 158
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 158
- 239000000956 alloy Substances 0.000 title claims abstract description 97
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 71
- 238000003860 storage Methods 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000003213 activating effect Effects 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 title claims abstract description 10
- 238000001994 activation Methods 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 30
- 230000004913 activation Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011232 storage material Substances 0.000 claims abstract description 20
- 239000006104 solid solution Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 13
- 150000004681 metal hydrides Chemical group 0.000 claims abstract description 13
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 229910004688 Ti-V Inorganic materials 0.000 claims abstract description 6
- 229910010968 Ti—V Inorganic materials 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 49
- 238000000498 ball milling Methods 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 5
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- 238000005303 weighing Methods 0.000 description 11
- 238000003723 Smelting Methods 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 3
- 229910000103 lithium hydride Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052774 Proactinium Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 titanium hydride Chemical compound 0.000 description 2
- 229910000048 titanium hydride Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910000047 yttrium hydride Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention provides a short-process preparation method for rapidly activating hydrogen storage alloy by utilizing hydrogen-containing compounds, and relates to the field of hydrogen storage materials. The method comprises the following steps: placing the hydrogen storage alloy material and the active auxiliary agent into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material; the hydrogen storage alloy material is selected from rare earth series AB X Titanium-iron-series AB type, titanium-zirconium-series AB type 2 Magnesium system A 2 One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder; the active auxiliary agent is metal hydride. The hydrogen storage material prepared by the method not only completes activationThe hydrogen can be absorbed and released without high-temperature or high-pressure activation, the production efficiency is improved, the production cost is reduced, and the original hydrogen storage capacity is maintained; the method is simple, quick and efficient, is particularly suitable for the activation process of the solid hydrogen storage material for the low-pressure hydrogenation station, and has important practical value for the application of the hydrogen storage alloy material to hydrogen energy engineering.
Description
Technical Field
The invention relates to the field of hydrogen storage materials, in particular to a short-flow preparation method for rapidly activating hydrogen storage alloy by utilizing hydrogen-containing compounds.
Background
Since the century, hydrogen energy has received extensive attention in terms of its clean combustion products and high calorific value. However, the construction of hydrogen fuel systems is still immature due to a number of technological challenges in the preparation, storage and use of hydrogen. Especially, the construction of hydrogen energy infrastructure becomes one of the key factors restricting the development of the hydrogen energy industry. The hydrogenation stations under construction and put into use are mainly based on high-pressure hydrogen storage technology, and the problems of limited hydrogenation capacity, high construction cost, service life of dynamic hydrogen compressors, maintenance and the like are faced in domestic market popularization.
The solid hydrogen storage alloy is a material for storing hydrogen into a solid material to realize hydrogen storage, and compared with a high-pressure gaseous and low-temperature liquid hydrogen storage method, the solid hydrogen storage alloy has the advantages of high volume hydrogen storage density, good safety, energy consumption reduction, capability of obtaining ultra-high-purity hydrogen and the like, and is suitable for being used as a hydrogen storage medium material in a hydrogenation station. However, in the hydrogen absorption process of the hydrogen storage alloy, hydrogen molecules are firstly absorbed on the surface of the hydrogen storage material and then dissociated into hydrogen atoms, and then enter into crystal lattices of the hydrogen storage alloy to form hydrides, so that the solid hydrogen storage alloy is subjected to activation treatment before use so as to achieve the best hydrogen absorption and desorption performance of the hydrogen storage alloy. The activation process is mainly divided into: vacuum activating or repeatedly absorbing and releasing hydrogen at low temperature and high pressure. However, these activation modes are relatively low in efficiency. For example, ferrotitanium-based hydrogen storage alloys require prolonged incubation and activation at high temperatures for up to several hours to several tens of hours before the alloy material absorbs hydrogen. The rare earth hydrogen storage material is usually pretreated and activated by heat treatment in the production process, but the heat treatment is usually followed by secondary activation by hydrogenation. Currently, a transition metal element (V, cr, mn, nb, zr, etc.) or a rare earth metal element (Ce, pr, nd, sm, ho, etc.) doping alternative method is generally adopted to improve the activation performance of the hydrogen storage alloy. No patent publication and article report on the method for activating the hydrogen storage alloy powder by using metal hydride as an auxiliary agent are known.
For a low-pressure hydrogenation station, the required hydrogen storage alloy material can reach more than ten thousand tons, and the activation process is a key technology which is promoted and needs to be mainly solved. When pure hydrogen is used for activation, the overall cost of the hydrogen storage material and the hydrogen storage device is greatly increased no matter what the activation process is in the hydrogen storage device or in the hydrogen storage material production process, and the overall requirement on the hydrogen storage device in the activation process is complicated. For example, if the device is large, both heat and mass transfer diffusion can be affected during activation; if the device design is too small, the device is limited by complex connection in the large-scale application of the hydrogen adding station. Therefore, the invention is a simple, quick and effective hydrogen storage alloy activation method, which is important for the large-scale application of the hydrogen storage alloy material in hydrogen energy engineering.
Disclosure of Invention
The invention aims to provide a short-flow preparation method for rapidly activating a hydrogen-containing alloy by utilizing hydrogen-containing compounds. The method is simple, quick and effective to improve the activation performance of the hydrogen storage material, so that the hydrogen storage material can directly meet the requirements of practical application.
In order to achieve the above purpose, the present invention may adopt the following technical scheme:
a short-flow preparation method for rapidly activating a hydrogen-containing alloy by using a hydrogen-containing compound, the method comprising:
placing the hydrogen storage alloy material and the active auxiliary agent into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material;
the hydrogen storage alloy material is selected from rare earth series AB X Titanium-iron-series AB type, titanium-zirconium-series AB type 2 Magnesium system A 2 One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder;
the active auxiliary agent is metal hydride.
Preferably, the metal hydride is selected from one or more of lithium hydride, magnesium hydride, aluminum hydride, titanium hydride and yttrium hydride.
Preferably, the active auxiliary agent accounts for (0.1-15)% of the mass of the main material.
Preferably, the hydrogen storage alloy powder has an average particle size of 100 to 300. Mu.m.
Preferably, the rare earth system AB X The pattern includes:
RENi x-a-b M a Mn b Al 0.1 wherein RE is one or more elements in La, ce, pr, nd, sm, gd; m is one or more elements of Cu, fe and Co; 5. more than or equal to x more than or equal to 4.5,1.0, more than or equal to a more than or equal to 0.1,1.0, more than or equal to b more than or equal to 0.1,1.5, more than or equal to a+b > 0;
or RE (RE) x Y y Ni z-a-b Mn a Al b Wherein RE is one or more elements in La, ce, pr, nd, sm, gd; x is more than 0, y is more than or equal to 0.5, and x+y=3; 12.5 More than or equal to z is more than or equal to 8.5,3.5, more than or equal to a+b is more than 0;2.0 More than or equal to a is more than or equal to 0.5, and more than or equal to 1.0 is more than or equal to b is more than or equal to 0.3.
Preferably, the solid solution type of titanium and vanadium includes:
TiV 2-x Mn x ，1.4≥x≥0.6；
or V x Ti y Cr z M v M is one or more elements in Mn, fe, zr, si, al; x+y+z+v=100, 50. Gtoreq.x.gtoreq.15, 40. Gtoreq.y.gtoreq.20, 40. Gtoreq.z.gtoreq. 20,1.0. Gtoreq.y/z.gtoreq.0.7, 15. Gtoreq.v.gtoreq.1.
Preferably, the hydrogen storage alloy material is TiV 1.1 Mn 0.9 Materials, laY 2 Ni 9.7 Mn 0.5 Al 0.3 Materials or La 0. 6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 A material.
Preferably, the uniform mixing mode is selected from one of high-energy ball milling, planetary ball milling, mechanical stirring, crushing and grinding.
Preferably, the weight ratio of the ball material is (0.5-50): 1, a step of; ball milling time is 10-300 min; the vibration frequency of the ball milling tank is 100-1500 rpm.
Preferably, the reaction atmosphere is one or more than two of hydrogen, helium, neon and argon.
The beneficial effects of the invention are that
The invention provides a short-process preparation method for rapidly activating hydrogen storage alloy by utilizing hydrogen-containing compounds, which takes metal hydride as an activating auxiliary agent, and can rapidly and effectively activate the hydrogen storage alloy material through uniform mixing; the hydrogen storage material prepared by the method not only completes the activation process, but also can absorb and release hydrogen without high-temperature or high-pressure activation process, thereby improving the production efficiency, reducing the production cost and simultaneously maintaining the original hydrogen storage capacity; the metal hydride is used as active assistant, which can deactivate the hydrogen storage alloy with atomic hydrogen and heat conducting the metal on the surface after hydrogen is released. The method is simple, quick and efficient, is particularly suitable for the activation process of the solid hydrogen storage material for the low-pressure hydrogenation station, and has important practical value for the application of the hydrogen storage alloy material to hydrogen energy engineering.
Drawings
FIG. 1 is a graph showing the first hydrogen absorption kinetics activation performance of the titanium vanadium solid solution systems of examples 1 and 2 and comparative example 1 of the present invention;
FIG. 2 is a rare earth AB of example 3 and comparative example 2, 3 of the present invention 3.5 A first hydrogen absorption kinetics activation performance diagram of the system;
FIG. 3 is a rare earth AB of inventive example 4 and comparative example 4, 5 5 And (3) a first hydrogen absorption kinetics activation performance diagram of the system.
Detailed Description
A short-flow preparation method for rapidly activating a hydrogen-containing alloy by using a hydrogen-containing compound, the method comprising:
placing the hydrogen storage alloy material and the active auxiliary agent into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material;
according to the present invention, the hydrogen storage alloy material is selected from the group consisting of rare earth series AB X Titanium-iron-series AB type, titanium-zirconium-series AB type 2 Magnesium system A 2 One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder;
the rare earth series AB X The pattern preferably includes:
RENi x-a-b M a Mn b Al 0.1 wherein RE is one or more elements in La, ce, pr, nd, sm, gd; m is one or more elements of Cu, fe and Co; 5. more than or equal to x more than or equal to 4.5,1.0, more than or equal to a more than or equal to 0.1,1.0, more than or equal to b more than or equal to 0.1,1.5, more than or equal to a+b > 0;
or RE (RE) x Y y Ni z-a-b Mn a Al b Wherein RE is one or more elements in La, ce, pr, nd, sm, gd; x is more than 0, y is more than or equal to 0.5, and x+y=3; 12.5 More than or equal to z is more than or equal to 8.5,3.5, more than or equal to a+b is more than 0;2.0 More than or equal to a is more than or equal to 0.5, and more than or equal to 1.0 is more than or equal to b is more than or equal to 0.3.
More preferably LaY 2 Ni 9.7 Mn 0.5 Al 0.3 Materials or La 0.6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 A material;
the titanium-vanadium solid solution type preferably includes:
TiV 2-x Mn x ，1.4≥x≥0.6；
or V x Ti y Cr z M v M is Mn, fe, ZOne or more elements of r, si and Al; x+y+z+v=100, 50. Gtoreq.x.gtoreq.15, 40. Gtoreq.y.gtoreq.20, 40. Gtoreq.z.gtoreq. 20,1.0. Gtoreq.y/z.gtoreq.0.7, 15. Gtoreq.v.gtoreq.1.
More preferably TiV 1.1 Mn 0.9 A material;
the average particle size of the hydrogen storage alloy powder is preferably 100-300 mu m. The hydrogen storage alloy material is prepared by a conventional method in the field.
According to the invention, the active auxiliary agent is a metal hydride, preferably one or more than two of lithium hydride, magnesium hydride, aluminum hydride, titanium hydride or yttrium hydride, more preferably lithium hydride, magnesium hydride or aluminum hydride; the metal hydride is used as active assistant to deactivate the hydrogen storage alloy with atomic hydrogen and to make the metal left after hydrogen is released have heat conducting effect.
According to the present invention, the coagent is present in an amount of 0.1 to 15% by mass, more preferably 1 to 8% by mass, based on the mass of the host material.
According to the present invention, the mode of uniform mixing is not particularly limited, and is preferably one selected from the group consisting of high-energy ball milling, planetary ball milling, mechanical stirring, pulverization, and grinding. The weight ratio of the ball material is preferably (0.5-50): 1, a step of; the ball milling time is preferably 10-300 min; the vibration frequency of the ball mill tank is preferably 100 to 1500 rpm.
According to the invention, the reaction atmosphere is preferably one or more than two of hydrogen, helium, neon and argon.
For further understanding of the present invention, the present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Example 1 a titanium vanadium solid solution system was prepared as follows:
(1) Vacuum-pumping the vacuum arc melting furnace to 2X 10 -3 0.5 atmosphere high purity argon with purity of 99.99% (volume percent) is filled into the mixture as protective gas after Pa, and Ti metal (purity is 99.7%), V metal (purity is 99.9%) and Mn metal (purity is 99.5%) are processed according to TiV 1.1 Mn 0.9 Weighing the chemical formula, putting into a vacuum arc furnace, and feedingAnd (3) smelting for 4 times at the arc current of 300A for 2min each time, naturally cooling and discharging to obtain alloy ingots, and crushing the alloy ingots to 50-150 mu m to obtain the alloy powder needing to be activated.
(2) Accurately weighing the TiV obtained in the step (1) according to the weight percentage 1.1 Mn 0.9 5g of material powder and 0.15g of commercial aluminum tri-hydride material, and putting the materials into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-to-material ratio is 5:1, the diameter of a steel ball is 4mm, the vibration frequency is 800 r/min, the ball milling time is 15min, the ball milling tank is taken down from the ball mill, the ball milling tank is opened in the air to obtain the titanium-vanadium solid solution hydrogen storage material, and the material is sealed and stored in a dryer.
The hydrogen absorbing kinetic performance measurement was performed by charging the hydrogen absorbing alloy material powder prepared in example 1 into a reactor, evacuating at 25℃for 30 minutes, and then charging high purity hydrogen gas of 99.99% purity (volume percent) at 4MPa into the reactor at 25 ℃. The resulting hydrogen absorption kinetics at 25℃is shown in FIG. 1 (wherein the abscissa represents time (in minutes) and the ordinate represents the amount of hydrogen absorption (in mass%).
Example 2 a titanium vanadium solid solution system was prepared as follows:
1) Vacuum-pumping the vacuum arc melting furnace to 2X 10 -3 0.5 atmosphere high purity argon with purity of 99.99% (volume percent) is filled into the mixture as protective gas after Pa, and Ti metal (purity is 99.7%), V metal (purity is 99.9%) and Mn metal (purity is 99.5%) are processed according to TiV 1.1 Mn 0.9 Weighing the chemical formula, putting the alloy ingot into a vacuum arc furnace for smelting, wherein the arc current is 300A, smelting for 4 times, smelting for 2 minutes each time, naturally cooling and discharging to obtain an alloy ingot, and crushing the alloy ingot to 50-150 mu m to obtain the hydrogen storage alloy powder to be activated.
(2) Accurately weighing the TiV obtained in the step (1) according to the weight percentage 1.1 Mn 0.9 5g of material powder and 0.40g of commercial aluminum tri-hydride material, and putting the materials into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-to-material ratio is 8:1, the diameter of the steel ball is 4mm, the vibration frequency is 800 rpm, the ball milling time is 15min, and the ball milling tank is used for ball millingTaking down on the machine, opening the ball milling tank titanium-vanadium solid solution hydrogen storage material in the air, and sealing and storing in a dryer.
The hydrogen storage alloy material powder prepared in example 2 was charged into a reactor, evacuated at 25 ℃ for 30 minutes, and then high purity hydrogen gas having a purity of 99.99% (volume percent) of 4MPa was charged into the reactor at 25 ℃ for hydrogen absorption kinetic performance measurement. The resulting hydrogen absorption kinetics at 25℃are shown in FIG. 1.
Comparative example 1
To further verify the activation performance of the above hydrogen storage alloy, a blank without the addition of metal hydride material was prepared at the same time as a comparison.
Weigh the same batch of TiV 1.1 Mn 0.9 5g of material powder, and putting the material powder into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the diameter of a steel ball is 4mm, and the ball-to-material ratio is 5:1, the vibration frequency is 800 revolutions per minute, the ball milling time is 15 minutes, the ball milling tank is taken down from the ball mill, the ball milling tank is opened in the air to obtain the titanium-vanadium solid solution hydrogen storage material, and the material is sealed and placed in a dryer for storage.
The titanium-vanadium solid solution hydrogen storage material prepared in comparative example 1 was vacuumized at 25 ℃ for 30 minutes, and then high-purity hydrogen with purity of 99.99% (volume percent) of 4MPa was charged into the reactor at 25 ℃ for hydrogen absorption kinetic performance measurement. The resulting hydrogen absorption kinetics at 25℃are shown in FIG. 1.
EXAMPLE 3 preparation of rare earth AB 3.5 The system is prepared by the following steps:
(1) Vacuum-pumping the vacuum arc melting furnace to 2X 10 -3 0.5 atmosphere high purity argon gas with purity of 99.99% (volume percent) is filled after Pa as protective gas, la metal (purity of 99.9%), Y metal (purity of 99.9%), ni metal (purity of 99.9%), mn metal (purity of 99.5%) and Al metal (purity of 99.5%) are mixed according to LaY 2 Ni 9.7 Mn 0.5 Al 0.3 Weighing the chemical formula, putting into a vacuum arc furnace for smelting, wherein the arc current is 300A, smelting for 4 times, smelting for 2min each time, naturally cooling and discharging to obtain an alloy ingot, crushing the alloy ingot to 50-150 mu m, and obtaining the alloy ingot to be activated and storedHydrogen alloy powder.
(2) Accurately weighing LaY obtained in the step (1) according to the weight percentage 2 Ni 9.7 Mn 0.5 Al 0.3 5g of material powder and 0.05g of commercial aluminum tri-hydride material, and putting the materials into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-to-material ratio is 5:1, the diameter of a steel ball is 4mm, the vibration frequency is 800 rpm, the ball milling time is 15min, a ball milling tank is taken down from a ball mill, the ball milling tank is opened in air to obtain a material to be tested, and the material to be tested is hermetically placed in a dryer for storage.
The hydrogen storage alloy material powder prepared in example 3 was charged into a reactor, evacuated at 25 ℃ for 30 minutes, and then high purity hydrogen gas having a purity of 99.99% (volume percent) of 4MPa was charged into the reactor at 25 ℃ for hydrogen absorption kinetic performance measurement. The resulting hydrogen absorption kinetics at 25℃is shown in FIG. 2 (wherein the abscissa represents time (in minutes) and the ordinate represents the amount of hydrogen absorption (in mass%).
Comparative example 2
To further verify the activation performance of the above hydrogen storage alloy, an annealed LaY alloy was prepared 2 Ni 9.7 Mn 0.5 Al 0.3 The alloy was activated at 70 c for comparison.
Weigh the same batch LaY 2 Ni 9.7 Mn 0.5 Al 0.3 20g of alloy ingot, annealing for 6 hours at 800 ℃, crushing the alloy ingot to 50-150 mu m to obtain hydrogen storage alloy powder, and sealing and storing in a dryer.
The hydrogen absorbing kinetic performance was measured by evacuating the hydrogen absorbing alloy powder prepared in comparative example 2 at 70℃for 30 minutes, and then charging 4MPa of high purity 99.99% (volume percent) hydrogen gas into the reactor at 70 ℃. The resulting hydrogen absorption kinetics at 70℃is shown in FIG. 2.
Comparative example 3
To further verify the activation performance of the above hydrogen storage alloy, an annealed LaY alloy was prepared 2 Ni 9.7 Mn 0.5 Al 0.3 The alloy is activated at 25 ℃ as a pairRatio.
Weigh the same batch LaY 2 Ni 9.7 Mn 0.5 Al 0.3 20g of alloy ingot, annealing for 6 hours at 800 ℃, crushing the alloy ingot to 50-150 mu m, weighing 5g of hydrogen storage alloy powder, and putting the alloy ingot into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the diameter of a steel ball is 4mm, and the ball-to-material ratio is 5:1, the vibration frequency is 800 r/min, the ball milling time is 15min, the ball milling pot is taken down from the ball mill, the material to be tested is opened in the air, and the material to be tested is sealed and placed in a dryer for preservation.
The hydrogen storage alloy material prepared in comparative example 3 was evacuated at 25 ℃ for 30 minutes, and then high purity hydrogen gas having a purity of 99.99% (by volume) of 4MPa was charged into the reactor at 25 ℃ for hydrogen absorption kinetics measurement. The resulting hydrogen absorption kinetics at 25℃are shown in FIG. 2.
EXAMPLE 4 preparation of rare earth AB 5 The system is prepared by the following steps:
(1) Vacuum-pumping the vacuum arc melting furnace to 2X 10 -3 0.5 atmosphere high purity argon gas with purity of 99.999% (volume percent) is filled after Pa as protective gas, la metal (purity of 99.9%), ce metal (purity of 99.9%), ni metal (purity of 99.9%), co metal (purity of 99.9%), mn metal (purity of 99.5%) and Al metal (purity of 99.5%) are mixed according to La 0.6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 Weighing the chemical formula, putting the alloy ingot into a vacuum arc furnace for smelting, wherein the arc current is 300A, smelting for 4 times, smelting for 2 minutes each time, naturally cooling and discharging to obtain an alloy ingot, and crushing the alloy ingot to 50-150 mu m to obtain the hydrogen storage alloy powder to be activated.
(2) Precisely weighing the La obtained in the step (1) according to the weight percentage 0.6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 5g of material powder and 0.10g of commercial magnesium hydride material, and putting the materials into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the ball-to-material ratio is 5:1, the diameter of a steel ball is 4mm, the vibration frequency is 800 rpm, the ball milling time is 15min, a ball milling tank is taken down from a ball mill, and the ball milling tank is opened in air to obtain a material to be measuredAnd sealing and storing in a dryer.
The hydrogen absorbing kinetic performance measurement was performed by charging the hydrogen absorbing alloy material powder prepared in example 4 into a reactor, evacuating at 25℃for 30 minutes, and then charging high purity hydrogen gas of 99.99% purity (volume percent) at 4MPa into the reactor at 25 ℃. The resulting hydrogen absorption kinetics at 25℃is shown in FIG. 3 (wherein the abscissa represents time (in minutes) and the ordinate represents the amount of hydrogen absorption (in mass%).
Comparative example 4
To further verify the activation performance of the above hydrogen storage alloy, an annealed La was prepared at the same time 0.6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 The alloy was activated at 25 c for comparison.
Weighing La of the same batch 0.6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 20g of alloy ingot, annealing for 4 hours at 600 ℃, crushing the alloy ingot to 50-150 mu m to obtain hydrogen storage alloy powder, and sealing and storing in a dryer.
The hydrogen absorbing kinetic properties were measured by evacuating the hydrogen absorbing alloy powder prepared in comparative example 4 at 25℃for 30 minutes, and then charging 4MPa of high purity 99.99% (volume percent) hydrogen gas into the reactor at 25 ℃. The resulting hydrogen absorption kinetics at 25℃is shown in FIG. 3.
Comparative example 5
To further verify the activation performance of the above hydrogen storage alloy, a blank without the addition of metal hydride material was prepared at the same time as a comparison.
Weighing La of the same batch 0.6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 5g of material powder, and putting the material powder into a stainless steel ball milling tank in a glove box filled with high-purity argon atmosphere, wherein the diameter of a steel ball is 4mm, and the ball-to-material ratio is 5:1, the vibration frequency is 800 r/min, the ball milling time is 15min, the ball milling tank is taken down from the ball mill, the ball milling tank is opened in the air to obtain the Ti-V solid solution hydrogen storage material, and the Ti-V solid solution hydrogen storage material is sealed and placed in a dryer for preservationAnd (5) storing.
The hydrogen absorbing kinetic performance was measured by evacuating the hydrogen absorbing alloy powder prepared in comparative example 5 at 25℃for 30 minutes, and then charging 4MPa of high purity 99.99% (volume percent) hydrogen gas into the reactor at 25 ℃. The resulting hydrogen absorption kinetics at 25℃is shown in FIG. 3.
Table 1 compares the activation performance of examples 1, 2, 3, 4 of the present invention with comparative examples 1, 2, 3, 4, 5, taking the hydrogen absorption time of 10 minutes as the cut-off point. As can be seen from Table 1, the hydrogen storage material system treated by the method of the invention can achieve larger hydrogen absorption capacity in a shorter time at 25 ℃ for the first time, and has excellent activation performance.
TABLE 1
Claims (5)
1. A short-flow preparation method for rapidly activating a hydrogen-containing alloy by using a hydrogen-containing compound, which is characterized by comprising the following steps:
placing the hydrogen storage alloy material and the active auxiliary agent into a container, and uniformly mixing in a reaction atmosphere to obtain an activated hydrogen storage alloy material;
the hydrogen storage alloy material is selected from rare earth series AB X Titanium-iron-series AB type, titanium-zirconium-series AB type 2 Magnesium system A 2 One or more of B-type and Ti-V solid solution type hydrogen storage alloy powder;
the active auxiliary agent accounts for (0.1-15)% of the mass of the main material;
the uniform mixing mode is high-energy ball milling;
the weight ratio of the ball materials of the high-energy ball mill is (0.5-50): 1, a step of; ball milling time is 10-300 min; the vibration frequency of the ball milling tank is 800-1500 rpm;
the reaction atmosphere is one or more than two of helium, neon and argon;
the active auxiliary agent is metal hydride, and the metal hydride is magnesium hydride or aluminum hydride;
the metal hydride is used as an active auxiliary agent, on one hand, atomic hydrogen is utilized to deactivate the hydrogen storage alloy, and on the other hand, the metal remained on the surface after the hydrogen is released has the heat conduction effect;
the method is used for the activation process of the solid hydrogen storage material for the low-pressure hydrogenation station.
2. The short-flow preparation method for rapidly activating a hydrogen-containing alloy according to claim 1, wherein the average particle size of the hydrogen-containing alloy powder is 100 to 300 μm.
3. The short-process preparation method for rapidly activating hydrogen-containing alloy according to claim 1, wherein the rare earth system AB X The pattern includes:
RENi x-a-b M a Mn b Al 0.1 wherein RE is one or more elements in La, ce, pr, nd, sm, gd; m is one or more elements of Cu, fe and Co; 5. more than or equal to x more than or equal to 4.5,1.0, more than or equal to a more than or equal to 0.1,1.0, more than or equal to b more than or equal to 0.1,1.5, more than or equal to a+b > 0;
or RE (RE) x Y y Ni z-a-b Mn a Al b Wherein RE is one or more elements in La, ce, pr, nd, sm, gd; x is more than 0, y is more than or equal to 0.5, and x+y=3; 12.5 More than or equal to z is more than or equal to 8.5,3.5, more than or equal to a+b is more than 0;2.0 More than or equal to a is more than or equal to 0.5, and more than or equal to 1.0 is more than or equal to b is more than or equal to 0.3.
4. The short-process preparation method for rapid activation of hydrogen-containing alloy according to claim 1, wherein the solid solution type of titanium vanadium comprises:
TiV 2-x Mn x ，1.4≥x≥0.6。
5. a method for utilizing hydrogen-containing compound according to claim 1The short-process preparation method of the activated hydrogen storage alloy is characterized in that the hydrogen storage alloy material is TiV 1.1 Mn 0.9 Materials, laY 2 Ni 9.7 Mn 0.5 Al 0.3 Materials or La 0.6 Ce 0.4 Ni 3.45 Co 0.75 Mn 0.7 Al 0.1 A material.
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